AP CHEMISTRY Scoring Guide

Unit 7 - Released FRQ Questions

1. Several reactions are carried out using AgBr, a cream-colored silver salt for which the value of the solubility-
product constant, Ksp , is 5.0 x 10−13 at 298 K.

a. Write the expression for the solubility-product constant, Ksp , of AgBr.

b. Calculate the value of [Ag+] in 50.0 mL of a saturated solution of AgBr at 298 K.

c. A 50.0 mL sample of distilled water is added to the solution described in part (b), which is in a beaker
with some solid AgBr at the bottom. The solution is stirred and equilibrium is reestablished. Some solid
AgBr remains in the beaker. Is the value of [Ag+] greater than, less than, or equal to the value you
calculated in part (b) ? Justify your answer.

d. Calculate the minimum volume of distilled water, in liters, necessary to completely dissolve a 5.0 g
sample of AgBr(s) at 298 K. (The molar mass of AgBr is 188 g mol-1.)

e. A student mixes 10.0 mL of 1.5 x 10−4 M AgNO3 with 2.0 mL of 5.0 x 10−4 M NaBr and stirs the
resulting mixture. What will the student observe? Justify your answer with calculations.

f. The color of another salt of silver, AgI(s), is yellow. A student adds a solution of NaI to a test tube
containing a small amount of solid, cream-colored AgBr. After stirring the contents of the test tube, the
student observes that the solid in the test tube changes color from cream to yellow.

i. Write the chemical equation for the reaction that occurred in the test tube.

ii. Which salt has the greater value of Ksp : AgBr or AgI ? Justify your answer.

Part A

1 point is earned for the correct expression (ion charges must be present; parentheses instead of square brackets not
accepted).

Ksp = [Ag+][Br−]

0 1

The student response earns one of the following points:

1 point is earned for the correct expression (ion charges must be present; parentheses instead of square brackets not
accepted).

Ksp = [Ag+][Br−]
Part B

1 point is earned for the correct value with support work (units not necessary).

Let x = equilibrium concentration of Ag+ (and of Br−).

AP Chemistry Page 1 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

Then Ksp = 5.0 x 10−13 = x2 ⇒ x = 7.1 x 10−7 M

0 1

The student response earns one of the following points:

1 point is earned for the correct value with support work (units not necessary).

Let x = equilibrium concentration of Ag+ (and of Br−).

Then Ksp = 5.0 x 10−13 = x2 ⇒ x = 7.1 x 10−7 M

1 point is earned for the correct answer with justification.

The value of [Ag+] after addition of distilled water is equal to the value in part (b). The concentration of ions in solution in
equilibrium with a solid does not depend on the volume of the solution.

0 1

The student response earns one of the following points:

1 point is earned for the correct answer with justification.

The value of [Ag+] after addition of distilled water is equal to the value in part (b). The concentration of ions in solution in
equilibrium with a solid does not depend on the volume of the solution.
Part D

1 point is earned for the calculation of moles of dissolved AgBr.

1 point is earned for the correct answer for the volume of water.

0 1 2

The student response earns two of the following points:

Page 2 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

1 point is earned for the calculation of moles of dissolved AgBr.

1 point is earned for the correct answer for the volume of water.

Part E

1 point is earned for calculation of concentration of ions.

1 point is earned for calculation of Q and conclusion based on comparison between Q and Ksp.

Q = [Ag+][Br−] = (1.3 x 10-4 M)(8.3 x 10-5 M) = 1.1 x 10-8

1 point is earned for indicating the precipitation of AgBr.

1.1 x 10-8 > 5.0 x 10-13, ∴ a precipitate will form.

0 1 2 3

The student response earns three of the following points:

1 point is earned for calculation of concentration of ions.

1 point is earned for calculation of Q and conclusion based on comparison between Q and Ksp.

Q = [Ag+][Br−] = (1.3 x 10-4 M)(8.3 x 10-5 M) = 1.1 x 10-8

1 point is earned for indicating the precipitation of AgBr.

1.1 x 10-8 > 5.0 x 10-13, ∴ a precipitate will form.

i. 1 point is earned for the correct equation.

AgBr(s) + I−(aq) → AgI(s) + Br−(aq)

AP Chemistry Page 3 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

OR

AgBr(s) + NaI(aq) → AgI(s) + NaBr(aq)

ii. 1 point is earned for the correct choice with justification.

AgBr has the greater value of Ksp. The precipitate will consist of the less soluble salt when both I−(aq) and
Br−(aq) are present. Because the color of the precipitate in the test tube turns yellow, it must be AgI(s) that
precipitates; therefore Ksp for AgBr must be greater than Ksp for AgI.

OR

Keq for the displacement reaction is . Because yellow AgI forms, Keq > 1; therefore Ksp of AgBr >
Ksp of AgI.

0 1 2

The student response earns two of the following points:

i. 1 point is earned for the correct equation.

AgBr(s) + I−(aq) → AgI(s) + Br−(aq)

OR

AgBr(s) + NaI(aq) → AgI(s) + NaBr(aq)

ii. 1 point is earned for the correct choice with justification.

AgBr has the greater value of Ksp. The precipitate will consist of the less soluble salt when both I−(aq) and
Br−(aq) are present. Because the color of the precipitate in the test tube turns yellow, it must be AgI(s) that
precipitates; therefore Ksp for AgBr must be greater than Ksp for AgI.

OR

Keq for the displacement reaction is . Because yellow AgI forms, Keq > 1; therefore Ksp of AgBr >
Ksp of AgI.

Page 4 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

2.

Ba2+(aq) + EDTA4- (aq) ⇄ Ba(EDTA)2- (aq) K = 7.7 × 107

The polyatomic ion C10H12N2O84- is commonly abbreviated as EDTA4-. The ion can form complexes with metal
ions in aqueous solutions. A complex of EDTA4- with Ba2+ ion forms according to the equation above. A 50.0 mL
volume of a solution that has an EDTA4- (aq) concentration of 0.30 M is mixed with 50.0 mL of 0.20 M
Ba(NO3)2 to produce 100.0 mL of solution.

a. Considering the value of K for the reaction, determine the concentration of Ba(EDTA)2- (aq) in the 100.0
mL of solution. Justify your answer.

b. The solution is diluted with distilled water to a total volume of 1.00 L. After equilibrium has been
reestablished, is the number of moles Ba2+(aq) of present in the solution greater than, less than, or equal
to the number of moles of Ba2+(aq) present in the original solution before it was diluted? Justify your
answer.

Part A

2 point(s) maximum

1 point is earned for indicating that the equilibrium concentration of Ba(EDTA)2- (aq) is the same as the original
concentration of Ba2+ when the solutions are mixed.

Based on the K value, the reaction goes essentially to completion. Ba2+(aq) is the limiting reactant.

The concentration of Ba2+ when the solutions are first mixed but before any reaction takes place is 0.20 M/2 =
0.10 M.

1 point is earned for the concentration with appropriate calculations.

Thus the equilibrium concentration of Ba(EDTA)2- (aq) is 0.10 M.

0 1 2

Student response earns 2 of the following 2 point(s)

2 point(s) maximum

1 point is earned for indicating that the equilibrium concentration of Ba(EDTA)2- (aq) is the same as the original
concentration of Ba2+ when the solutions are mixed.

Based on the K value, the reaction goes essentially to completion. Ba2+(aq) is the limiting reactant.

The concentration of Ba2+ when the solutions are first mixed but before any reaction takes place is 0.20 M/2 =
0.10 M.

AP Chemistry Page 5 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

1 point is earned for the concentration with appropriate calculations.

Thus the equilibrium concentration of Ba(EDTA)2- (aq) is 0.10 M.

2 point(s) maximum

1 point is earned for stating that the number of moles of Ba2+(aq) will increase.

1 point is earned for a valid justification.

The number of moles of Ba2+(aq) increases because the percent dissociation of Ba(EDTA)2-(aq) increases as
the solution is diluted.

OR

A mathematical justification such as the following:

The dilution from 100.0 mL to 1.00 L reduces the concentrations of all species to one tenth of their original
values.

Immediately after the dilution, the reaction quotient, Q, can be determined as shown below

Because Q > K, the net reaction will produce more reactants to move toward equilibrium, so the number of
moles of Ba2+(aq) will be greater than the number in the original solution.

0 1 2

Student response earns 2 of the following 2 point(s)

2 point(s) maximum

1 point is earned for stating that the number of moles of Ba2+(aq) will increase.

1 point is earned for a valid justification.

The number of moles of Ba2+(aq) increases because the percent dissociation of Ba(EDTA)2-(aq) increases as
the solution is diluted.

OR

Page 6 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

A mathematical justification such as the following:

The dilution from 100.0 mL to 1.00 L reduces the concentrations of all species to one tenth of their original
values.

Immediately after the dilution, the reaction quotient, Q, can be determined as shown below

Because Q > K, the net reaction will produce more reactants to move toward equilibrium, so the number of
moles of Ba2+(aq) will be greater than the number in the original solution.

AP Chemistry Page 7 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

3. The compound butane, C4H10 , occurs in two isomeric forms, n-butane and isobutane (2-methyl propane). Both
compounds exist as gases at 25°C and 1.0 atm.

a. Draw the structural formula of each of the isomers (include all atoms). Clearly label each structure.

b. On the basis of molecular structure, identify the isomer that has the higher boiling point. Justify your
answer.

The two isomers exist in equilibrium as represented by the equation below.

n-butane(g) ⇄ isobutane(g) Kc = 2.5 at 25°C

Suppose that a 0.010 mol sample of pure n-butane is placed in an evacuated 1.0 L rigid container at 25°C.

c. Write the expression for the equilibrium constant, Kc , for the reaction.

d. Calculate the initial pressure in the container when the n-butane is first introduced (before the reaction
starts).

e. The n-butane reacts until equilibrium has been established at 25°C.

i. Calculate the total pressure in the container at equilibrium. Justify your answer.

ii. Calculate the molar concentration of each species at equilibrium.

iii. If the volume of the system is reduced to half of its original volume, what will be the new
concentration of n-butane after equilibrium has been reestablished at 25°C ? Justify your
answer.

Suppose that in another experiment a 0.010 mol sample of pure isobutane is placed in an evacuated 1.0 L
rigid container and allowed to come to equilibrium at 25°C.

f. Calculate the molar concentration of each species after equilibrium has been established.

Part A

2 points are earned for two correct structures with correct labels

Page 8 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

(Note: 1 point can be earned for either two correct structures that are mislabeled or one correct structure with or without
correct label.)

OR

1 point can be earned for two skeletal structures (hydrogen atoms not shown) with proper labels.

0 1 2

The student response earns two of the following points:

2 points are earned for two correct structures with correct labels

(Note: 1 point can be earned for either two correct structures that are mislabeled or one correct structure with or without
correct label.)

OR

AP Chemistry Page 9 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

1 point can be earned for two skeletal structures (hydrogen atoms not shown) with proper labels.
Part B

1 point is earned for the correct choice of isomer with justification.

The isomer n-butane has the higher boiling point. London (dispersion) forces are greater among molecules of n-butane
than they are among molecules of isobutane because molecules of n-butane, with its linear structure, can approach one
another more closely and can form a greater number of induced temporary dipoles than molecules of isobutane, with its
more compact structure, can form.

0 1

The student response earns one of the following points:

1 point is earned for the correct choice of isomer with justification.

The isomer n-butane has the higher boiling point. London (dispersion) forces are greater among molecules of n-butane
than they are among molecules of isobutane because molecules of n-butane, with its linear structure, can approach one
another more closely and can form a greater number of induced temporary dipoles than molecules of isobutane, with its
more compact structure, can form.
Part C

1 point is earned for the correct equation.

0 1

The student response earns one of the following points:

1 point is earned for the correct equation.

Part D

1 point is earned for the correct substitution and numerical answer.

= 0.24 atm

Page 10 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

0 1

The student response earns one of the following points:

1 point is earned for the correct substitution and numerical answer.

= 0.24 atm
Part E

i. 1 point is earned for the correct answer with justification.

The total pressure in the container remains the same, 0.24 atm. As the reaction proceeds, the number of
molecules in the container remains constant; one molecule of isobutane is produced for each molecule of
n-butane consumed.

ii. 1 point is earned for the correct setup.

1 point is earned for both correct numerical answers.

x = 2.5 (0.010 – x) = 0.025 – 2.5x

3.5x = 0.025 ⇒ x = 0.0071 M isobutane

(0.010 M – 0.0071 M) = 0.003 M n-butane

iii. 1 point is earned for the correct answer with justification.

Halving the volume of the container at equilibrium doubles the pressure of both isobutane and n-butane, which
has no effect on the equilibrium because the stoichiometry of the reaction is one mole of product produced for
each mole of reactant consumed. Since the number of moles of each isomer is unchanged but the volume is
reduced by half, concentrations of both isomers are doubled and the concentration of n-butane will be 2 x 0.003
M = 0.006 M.

0 1 2 3 4

The student response earns four of the following points:

i. 1 point is earned for the correct answer with justification.

AP Chemistry Page 11 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

The total pressure in the container remains the same, 0.24 atm. As the reaction proceeds, the number of
molecules in the container remains constant; one molecule of isobutane is produced for each molecule of
n-butane consumed.

ii. 1 point is earned for the correct setup.

1 point is earned for both correct numerical answers.

x = 2.5 (0.010 – x) = 0.025 – 2.5x

3.5x = 0.025 ⇒ x = 0.0071 M isobutane

(0.010 M – 0.0071 M) = 0.003 M n-butane

iii. 1 point is earned for the correct answer with justification.

Halving the volume of the container at equilibrium doubles the pressure of both isobutane and n-butane, which
has no effect on the equilibrium because the stoichiometry of the reaction is one mole of product produced for
each mole of reactant consumed. Since the number of moles of each isomer is unchanged but the volume is
reduced by half, concentrations of both isomers are doubled and the concentration of n-butane will be 2 x 0.003
M = 0.006 M.
Part F

1 point is earned for correct numerical answers or a correct statement regarding their equivalence to values obtained in
part (e)(ii).

The concentrations of isobutane and n-butane would be the same as they were calculated in part (e)(ii), 0.0071 M and
0.003 M, respectively.

0 1

The student response earns one of the following points:

1 point is earned for correct numerical answers or a correct statement regarding their equivalence to values obtained in
part (e)(ii).

The concentrations of isobutane and n-butane would be the same as they were calculated in part (e)(ii), 0.0071 M and
0.003 M, respectively.

Page 12 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

4. C(s) + CO2(g) ⇄ 2 CO(g)

Solid carbon and carbon dioxide gas at 1,160 K were placed in a rigid 2.00 L container, and the reaction
represented above occurred. As the reaction proceeded, the total pressure in the container was monitored. When
equilibrium was reached, there was still some C(s) remaining in the container. Results are recorded in the table
below.

(a) Write the expression for the equilibrium constant, Kp , for the reaction.

(b) Calculate the number of moles of CO2(g) initially placed in the container. (Assume that the volume of the solid
carbon is negligible.)

(c) For the reaction mixture at equilibrium at 1,160 K, the partial pressure of the CO2(g) is 1.63 atm. Calculate

(i) the partial pressure of CO(g) , and

(d) If a suitable solid catalyst were placed in the reaction vessel, would the final total pressure of the gases at
equilibrium be greater than, less than, or equal to the final total pressure of the gases at equilibrium without the
catalyst? Justify your answer. (Assume that the volume of the solid catalyst is negligible.)

In another experiment involving the same reaction, a rigid 2.00 L container initially contains 10.0 g of C(s), plus
CO(g) and CO2(g), each at a partial pressure of 2.00 atm at 1,160 K.

(e) Predict whether the partial pressure of CO2(g) will increase, decrease, or remain the same as this system
approaches equilibrium. Justify your prediction with a calculation.

Part A

1 point is earned for correct expression.

AP Chemistry Page 13 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

0 1

The student response earns one of the following points:

1 point is earned for correct expression.

Part B

1 point is earned for correct setup.

1 point is earned for the correct answer.

0 1 2

The student response earns two of the following points:

1 point is earned for correct setup.

1 point is earned for the correct answer.

Part C

(i)

1 point is earned for correct answer supported by correct method.

(ii)

1 point is earned for a correct setup that is consistent with part (a).

1 point is earned for the correct answer according to the setup.

Page 14 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

0 1 2 3

The student response earns three of the following points:

(i)

1 point is earned for correct answer supported by correct method.

(ii)

1 point is earned for a correct setup that is consistent with part (a).

1 point is earned for the correct answer according to the setup.

Part D

1 point is earned for the correct answer with justification.

The total pressure of the gases at equilibrium with a catalyst present would be equal to the total pressure of the gases
without a catalyst. Although a catalyst would cause the system to reach the same equilibrium state more quickly, it would
not affect the extent of the reaction, which is determined by the value of the equilibrium constant, Kp.

0 1

The student response earns one of the following points:

1 point is earned for the correct answer with justification.

The total pressure of the gases at equilibrium with a catalyst present would be equal to the total pressure of the gases
without a catalyst. Although a catalyst would cause the system to reach the same equilibrium state more quickly, it would
not affect the extent of the reaction, which is determined by the value of the equilibrium constant, Kp.
Part E

1 point is earned for a correct calculation involving Q or ICE calculation.

1 point is earned for a correct conclusion based on the calculation.

AP Chemistry Page 15 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

therefore will decrease as the system approaches equilibrium.

0 1 2

The student response earns two of the following points:

1 point is earned for a correct calculation involving Q or ICE calculation.

1 point is earned for a correct conclusion based on the calculation.

therefore will decrease as the system approaches equilibrium.

Page 16 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

5. Answer the following questions about the solubility of Ca(OH)2 (Ksp = 1.3 x 10-6 ) .

a. Write a balanced chemical equation for the dissolution of Ca(OH)2(s) in pure water.

b. Calculate the molar solubility of Ca(OH)2 in 0.10 M Ca(NO3)2 .

c. In the box below, complete a particle representation diagram that includes four water molecules with
proper
orientation around the Ca2+ ion.

Represent water molecules as .

Part A

1 point is earned for the correct equation.

Ca(OH)2 ⇄ Ca2+ + 2 OH-

0 1

The student response earns one of the following points:

1 point is earned for the correct equation.

AP Chemistry Page 17 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

Ca(OH)2 ⇄ Ca2+ + 2 OH-

1 point is earned for the correct stoichiometry and setup.

Ksp = [Ca2+] [OH-]2

1.3 x 10-6 = (0.10 + x) (2x)2 ≈ (0.10) 4x2 [assuming x << 0.10]

1.3 x 10-5 = 4x2

x = 0.0018 M

1 point is earned for the final answer.

Molar solubility of Ca(OH)2 = 0.0018 M

0 1 2

The student response earns two of the following points:

1 point is earned for the correct stoichiometry and setup.

Ksp = [Ca2+] [OH-]2

1.3 x 10-6 = (0.10 + x) (2x)2 ≈ (0.10) 4x2 [assuming x << 0.10]

1.3 x 10-5 = 4x2

x = 0.0018 M

1 point is earned for the final answer.

Molar solubility of Ca(OH)2 = 0.0018 M

1 point is earned for a correct diagram that shows at least three of the four water molecules oriented as described.

Page 18 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

[The diagram should show the oxygen side of the water molecules oriented closer to the Ca2+ ion.]

0 1

The student response earns one of the following points:

1 point is earned for a correct diagram that shows at least three of the four water molecules oriented as described.

[The diagram should show the oxygen side of the water molecules oriented closer to the Ca2+ ion.]

AP Chemistry Page 19 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

6. CaCO3(s) ⇄ CaO(s)+ CO2(g)

When heated, calcium carbonate decomposes according to the equation above. In a study of the decomposition of
calcium carbonate, a student added a 50.0 g sample of powdered CaCO3(s) to a 1.00 L rigid container. The student
sealed the container, pumped out all the gases, then heated the container in an oven at 1100 K. As the container
was heated, the total pressure of the CO2(g) in the container was measured over time. The data are plotted in the
graph below.

The student repeated the experiment, but this time the student used a 100.0 g sample of powdered CaCO3(s). In
this experiment, the final pressure in the container was 1.04 atm, which was the same final pressure as in the first
experiment.

a. Calculate the number of moles of CO2(g) present in the container after 20 minutes of heating.

b. The student claimed that the final pressure in the container in each experiment became constant because
all of the CaCO3(s) had decomposed. Based on the data in the experiments, do you agree with this claim?
Explain.

c. After 20 minutes some CO2(g) was injected into the container, initially raising the pressure to 1.5 atm.
Would the final pressure inside the container be less than, greater than, or equal to 1.04 atm? Explain
your reasoning.

d. Are there sufficient data obtained in the experiments to determine the value of the equilibrium constant,
Kp ,for the decomposition of CaCO3(s) at 1100 K? Justify your answer.

Part A

1 point is earned for the proper setup using the ideal gas law and an answer that is consistent with the setup.

PV = nRT

Page 20 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

0 1

The student response earns one of the following points:

1 point is earned for the proper setup using the ideal gas law and an answer that is consistent with the setup.

PV = nRT

Part B

1 point is earned for disagreement with the claim and for a correct justification using stoichiometry or a discussion of the
creation of an equilibrium condition.

Do not agree with claim

Explanation I: In experiment 1, the moles of CaCO3 = 50.0 g/100.09 g/mol = 0.500 mol CaCO3. If the reaction had gone
to completion, 0.500 mol of CO2 would have been produced. From part (a) only 0.0115 mol was produced. Hence, the
student's claim was false.

Explanation II: The two different experiments (one with 50.0 g of CaCO3 and one with 100.0 g of CaCO3) reached the
same constant, final pressure of 1.04 atm. Since increasing the amount of reactant did not produce more product, there is
no way that all of the CaCO3 reacted. Instead, an equilibrium condition has been achieved and there must be some solid
CaCO3 in the container.

0 1

The student response earns one of the following points:

1 point is earned for disagreement with the claim and for a correct justification using stoichiometry or a discussion of the
creation of an equilibrium condition.

Do not agree with claim

Explanation I: In experiment 1, the moles of CaCO3 = 50.0 g/100.09 g/mol = 0.500 mol CaCO3. If the reaction had gone
to completion, 0.500 mol of CO2 would have been produced. From part (a) only 0.0115 mol was produced. Hence, the
student's claim was false.

Explanation II: The two different experiments (one with 50.0 g of CaCO3 and one with 100.0 g of CaCO3) reached the
same constant, final pressure of 1.04 atm. Since increasing the amount of reactant did not produce more product, there is
no way that all of the CaCO3 reacted. Instead, an equilibrium condition has been achieved and there must be some solid
CaCO3 in the container.

AP Chemistry Page 21 of 37
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Unit 7 - Released FRQ Questions

Part C

1 point is earned for the correct answer with justification.

The final pressure would be equal to 1.04 atm. Equilibrium was reached in both experiments; the equilibrium pressure at
this temperature is 1.04 atm. As the reaction shifts toward the reactant, the amount of CO2(g) in the container will
decrease until the pressure returns to 1.04 atm.

0 1

The student response earns one of the following points:

1 point is earned for the correct answer with justification.

The final pressure would be equal to 1.04 atm. Equilibrium was reached in both experiments; the equilibrium pressure at
this temperature is 1.04 atm. As the reaction shifts toward the reactant, the amount of CO2(g) in the container will
decrease until the pressure returns to 1.04 atm.
Part D

1 point is earned for correct explanation that is consistent with the student's answer to part (b).

Yes. For the equilibrium reaction represented by the chemical equation in this problem, at a given temperature the
equilibrium pressure of CO2 determines the equilibrium constant. Since the measured pressure of CO2 is also the
equilibrium pressure of CO2, .

Note: If the response in part (b) indicates "yes", that all of the CaCO3(s) had decomposed, then the point can be earned by
stating that the system did not reach equilibrium in either experiment and hence the value of Kp cannot be calculated from
the data.

0 1

The student response earns one of the following points:

1 point is earned for correct explanation that is consistent with the student's answer to part (b).

Yes. For the equilibrium reaction represented by the chemical equation in this problem, at a given temperature the
equilibrium pressure of CO2 determines the equilibrium constant. Since the measured pressure of CO2 is also the
equilibrium pressure of CO2, .

Note: If the response in part (b) indicates "yes", that all of the CaCO3(s) had decomposed, then the point can be earned by
stating that the system did not reach equilibrium in either experiment and hence the value of Kp cannot be calculated from
the data.

Page 22 of 37 AP Chemistry
 Scoring Guide

Unit 7 - Released FRQ Questions

7. Answer the following questions about the thermodynamics of the reactions represented below.

Reaction X: ½ I2(s) + ½ Cl2(g) ⇄ ICl(g) ∆H°f = 18 kJ mol–1, ∆S°298 = 78 J K–1 mol–1

Reaction Y: ½ I2(s) + ½ Br2(l) ⇄ IBr(g) ∆H°f = 41 kJ mol–1, ∆S°298 = 124 J K–1 mol–1

a. Is reaction X , represented above, spontaneous under standard conditions? Justify your answer with a
calculation.

b. Calculate the value of the equilibrium constant, Keq , for reaction X at 25℃.

c. What effect will an increase in temperature have on the equilibrium constant for reaction X ? Explain
your answer.

d. Explain why the standard entropy change is greater for reaction Y than for reaction X.

e. Above what temperature will the value of the equilibrium constant for reaction Y be greater than 1.0 ?
Justify your answer with calculations.

f. For the vaporization of solid iodine, I2(s) → I2(g) , the value of ∆H°298 is 62 kJ mol–1. Using this
information, calculate the value of ∆H°298 for the reaction represented below.

I2(g) + Cl2(g) ⇄ 2 ICl(g)

Part A

1 point is earned for the correct value of ∆G°.

∆G° = ∆H° – T∆S°

= (18 kJ mol−1) − ( 298 K)(0.078 kJ mol−1 K−1) = −5 kJ mol−1

1 point is earned for a correct justification of spontaneity.

Reaction is spontaneous because ∆G° < 0.

0 1 2

The student response earns two of the following points:

1 point is earned for the correct value of ∆G°.

∆G° = ∆H° – T∆S°

= (18 kJ mol−1) − ( 298 K)(0.078 kJ mol−1 K−1) = −5 kJ mol−1

1 point is earned for a correct justification of spontaneity.

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Unit 7 - Released FRQ Questions

Reaction is spontaneous because ∆G° < 0.

1 point is earned for the correct answer.

Keq = e2.019 = (7.5314) = 8

0 1

The student response earns one of the following points:

1 point is earned for the correct answer.

Keq = e2.019 = (7.5314) = 8

1 point is earned for the correct choice with a correct explanation.

Since ∆H° is positive, an increase in T will cause −∆H°/RT to become a smaller negative number, therefore Keq will
increase.

OR

The reaction is endothermic (∆H = +18 kJ mol−1); an increase in temperature shifts the reaction to favor more products
relative to the reactants, resulting in an increase in the value of Keq.

0 1

The student response earns one of the following points:

1 point is earned for the correct choice with a correct explanation.

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Unit 7 - Released FRQ Questions

Since ∆H° is positive, an increase in T will cause −∆H°/RT to become a smaller negative number, therefore Keq will
increase.

OR

The reaction is endothermic (∆H = +18 kJ mol−1); an increase in temperature shifts the reaction to favor more products
relative to the reactants, resulting in an increase in the value of Keq.
Part D

1 point is earned for a correct explanation.

Both reaction X and reaction Y have solid iodine as a reactant, but the second reactant in reaction X is chlorine gas
whereas the second reactant in reaction Y is liquid bromine. Liquids have lower entropies than gases, thus in reaction Y the
reactants are more ordered (and have lower entropies) than in reaction X . The products of both reaction X and reaction Y
have about the same disorder, so the change in entropy from reactants to products is greater in reaction Y than in reaction
X.

0 1

The student response earns one of the following points:

1 point is earned for a correct explanation.

Both reaction X and reaction Y have solid iodine as a reactant, but the second reactant in reaction X is chlorine gas
whereas the second reactant in reaction Y is liquid bromine. Liquids have lower entropies than gases, thus in reaction Y the
reactants are more ordered (and have lower entropies) than in reaction X . The products of both reaction X and reaction Y
have about the same disorder, so the change in entropy from reactants to products is greater in reaction Y than in reaction
X.
Part E

1 point is earned for ∆G° = 0.

∆G° = ∆H° – T∆S°

Keq = 1 when ∆G° = 0 ⇒ T∆S° = ∆H° ⇒

1 point is earned for the correct temperature.

So when T > 330 K, ∆G° < 0 kJ mol–1 ⇒ Keq > 1.0

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Unit 7 - Released FRQ Questions

0 1 2

The student response earns two of the following points:

1 point is earned for ∆G° = 0.

∆G° = ∆H° – T∆S°

Keq = 1 when ∆G° = 0 ⇒ T∆S° = ∆H° ⇒

1 point is earned for the correct temperature.

So when T > 330 K, ∆G° < 0 kJ mol–1 ⇒ Keq > 1.0

1 point is earned for ∆H°298 of either the first or second equation.

1 point is earned for the correct sum of the ∆H°298 values.

I2(s) + Cl2(g) ⇄ 2 ICl(g) ∆H°298 = 2 x 18 kJ mol−1

I2(g) ⇄ I2(s) ∆H°298 = − 62 kJ mol−1

________________________________________________

I2(g) + Cl2(g) ⇄ 2 ICl(g) ∆H°298 = −26 kJ mol−1

0 1 2

The student response earns two of the following points:

1 point is earned for ∆H°298 of either the first or second equation.

1 point is earned for the correct sum of the ∆H°298 values.

I2(s) + Cl2(g) ⇄ 2 ICl(g) ∆H°298 = 2 x 18 kJ mol−1

I2(g) ⇄ I2(s) ∆H°298 = − 62 kJ mol−1

________________________________________________

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Unit 7 - Released FRQ Questions

I2(g) + Cl2(g) ⇄ 2 ICl(g) ∆H°298 = −26 kJ mol−1

8.

A student is given the task of determining the I- content of tablets that contain KI and an inert, water-soluble sugar
as a filler. A tablet is dissolved in 50.0 mL of distilled water, and an excess of 0.20 M Pb(NO3)2(aq) is added to
the solution. A yellow precipitate forms, which is then filtered, washed, and dried. The data from the experiment
are shown in the table above.

a. For the chemical reaction that occurs when the precipitate forms,

i. write a balanced, net-ionic equation for the reaction, and

ii. explain why the reaction is best represented by a net-ionic equation.

b. Explain the purpose of drying and weighing the filter paper with the precipitate three times.

c. In the filtrate solution, is [K+] greater than, less than, or equal to [NO3−] ? Justify your answer.

d. Calculate the number of moles of precipitate that is produced in the experiment.

e. Calculate the mass percent of I- in the tablet.

f. In another trial, the student dissolves a tablet in 55.0 mL of water instead of 50.0 mL of water. Predict
whether the experimentally determined mass percent of I− will be greater than, less than, or equal to the
amount calculated in part (e). Justify your answer.

g. A student in another lab also wants to determine the I− content of a KI tablet but does not have access to
Pb(NO3)2 . However, the student does have access to 0.20 M AgNO3 , which reacts with I− (aq) to
produce AgI(s). The value of Ksp for AgI is 8.5 x 10−17.

i. Will the substitution of AgNO3 for Pb(NO3)2 result in the precipitation of the I− ion from
solution? Justify your answer.

ii. The student only has access to one KI tablet and a balance that can measure to the nearest 0.01
g. Will the student be able to determine the mass of AgI produced to three significant figures?
Justify your answer.

Part A

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Unit 7 - Released FRQ Questions

i. 1 point is earned for a balanced net-ionic equation.

Pb2+ + 2 I- → PbI2

ii. 1 point is earned for a valid explanation.

The net-ionic equation shows the formation of the PbI2(s) from Pb2+(aq) and I-(aq) ions, omitting the non-
reacting species (spectator ions), K+(aq) and NO3-(aq).

0 1 2

The student response earns two of the following points:

i. 1 point is earned for a balanced net-ionic equation.

Pb2+ + 2 I- → PbI2

ii. 1 point is earned for a valid explanation.

The net-ionic equation shows the formation of the PbI2(s) from Pb2+(aq) and I-(aq) ions, omitting the non-
reacting species (spectator ions), K+(aq) and NO3-(aq).
Part B

1 point is earned for a valid explanation.

The filter paper and precipitate must be dried several times (to a constant mass) to ensure that all the water has been
driven off.

0 1

The student response earns one of the following points:

1 point is earned for a valid explanation.

The filter paper and precipitate must be dried several times (to a constant mass) to ensure that all the water has been
driven off.
Part C

1 point is earned for a correct comparison with a valid explanation.

[K+] is less than [NO3-] because the source of the NO3-, the 0.20 M Pb(NO3)2(aq), was added in excess.

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Unit 7 - Released FRQ Questions

0 1

The student response earns one of the following points:

1 point is earned for a correct comparison with a valid explanation.

[K+] is less than [NO3-] because the source of the NO3-, the 0.20 M Pb(NO3)2(aq), was added in excess.
Part D

1 point is earned for the correct number of moles of PbI2(s) precipitate.

1.698 g – 1.462 g = 0.236 g PbI2(s)

0 1

The student response earns one of the following points:

1 point is earned for the correct number of moles of PbI2(s) precipitate.

1.698 g – 1.462 g = 0.236 g PbI2(s)

Part E

1 point is earned for determining the number of moles of I- in one tablet.

1 point is earned for calculating the mass percent of I- in the KI tablet.

0 1 2

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Unit 7 - Released FRQ Questions

The student response earns two of the following points:

1 point is earned for determining the number of moles of I- in one tablet.

1 point is earned for calculating the mass percent of I- in the KI tablet.

Part F

1 point is earned for correct comparison with a valid justification.

The mass percent of I- will be the same. Pb2+(aq) was added in excess, ensuring that essentially no I- remained in
solution. The additional water is removed by filtration and drying, leaving the same mass of dried precipitate.

0 1

The student response earns one of the following points:

1 point is earned for correct comparison with a valid justification.

The mass percent of I- will be the same. Pb2+(aq) was added in excess, ensuring that essentially no I- remained in
solution. The additional water is removed by filtration and drying, leaving the same mass of dried precipitate.
Part G

i. 1 point is earned for the correct answer with a valid justification.

Yes. Addition of an excess of 0.20 M AgNO3(aq) will precipitate all of the I- ion present in the solution because
AgI is insoluble, as evidenced by its low value of Ksp.

ii. 1 point is earned for a correct answer with a valid justification.

No. If masses can be measured to ±0.01 g, then the mass of the dry AgI(s) precipitate (which is less than 1 g) will
be known to only two significant figures.

0 1 2

The student response earns two of the following points:

i. 1 point is earned for the correct answer with a valid justification.

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Unit 7 - Released FRQ Questions

Yes. Addition of an excess of 0.20 M AgNO3(aq) will precipitate all of the I- ion present in the solution because
AgI is insoluble, as evidenced by its low value of Ksp.

ii. 1 point is earned for a correct answer with a valid justification.

No. If masses can be measured to ±0.01 g, then the mass of the dry AgI(s) precipitate (which is less than 1 g) will
be known to only two significant figures.

9. Answer the following questions about nitrogen, hydrogen, and ammonia.

a. In the boxes below, draw the complete Lewis electron-dot diagrams for N2 and NH3 .

b. Calculate the standard free-energy change, ΔG°, that occurs when 12.0 g of H2(g) reacts with excess
N2(g) at 298 K according to the reaction represented below.

N2(g) + 3 H2(g) ⇄ 2 NH3(g) 298 ΔG°298 = –34 kJ mol-1

c. Given that ΔH°298 for the reaction is −92.2 kJ mol-1, which is larger, the total bond dissociation energy
of the reactants or the total bond dissociation energy of the products? Explain.

d. The value of the standard entropy change, ΔS°298 , for the reaction is −199 J mol-1K-1. Explain why the
value of ΔS°298 is negative.

e. Assume that ΔH° and ΔS° for the reaction are independent of temperature.

i. Explain why there is a temperature above 298 K at which the algebraic sign of the value of ΔG°
changes.

ii. Theoretically, the best yields of ammonia should be achieved at low temperatures and high
pressures.

Part A

2 points are earned for the correct Lewis electron-dot diagrams (1 point each).

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Unit 7 - Released FRQ Questions

The correct structures are shown in the boxes above.

0 1 2

The student response earns two of the following points:

2 points are earned for the correct Lewis electron-dot diagrams (1 point each).

The correct structures are shown in the boxes above.

1 point is earned for the correct stoichiometry.

1 point is earned for the correct answer.

0 1 2

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Unit 7 - Released FRQ Questions

The student response earns two of the following points:

1 point is earned for the correct stoichiometry.

1 point is earned for the correct answer.

Part C

1 point is earned for the correct answer with the correct equation and explanation.

ΔH°298 = Σ (bond energy of the reactants) − Σ (bond energy of the products) Based on the equation above, for ΔH°298
to be negative, the total bond energy of the products must be larger than the total bond energy of the reactants.

OR

More energy is released as product bonds are formed than is absorbed as reactant bonds are broken.

0 1

The student response earns one of the following points:

1 point is earned for the correct answer with the correct equation and explanation.

ΔH°298 = Σ (bond energy of the reactants) − Σ (bond energy of the products) Based on the equation above, for ΔH°298
to be negative, the total bond energy of the products must be larger than the total bond energy of the reactants.

OR

More energy is released as product bonds are formed than is absorbed as reactant bonds are broken.
Part D

1 point is earned for the correct explanation.

All of the reactants and products in the reaction are in the gas phase, so the sign of the entropy change will depend on the
number of moles of particles in the reactants and products. There are more moles of reactants (four) compared with moles
of products (two), so there is a greater number of microstates in the reactants than in the products. Therefore the entropy
decreases as the reaction proceeds (fewer possible microstates), and the sign of the entropy change is negative.

0 1

The student response earns one of the following points:

1 point is earned for the correct explanation.

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Unit 7 - Released FRQ Questions

All of the reactants and products in the reaction are in the gas phase, so the sign of the entropy change will depend on the
number of moles of particles in the reactants and products. There are more moles of reactants (four) compared with moles
of products (two), so there is a greater number of microstates in the reactants than in the products. Therefore the entropy
decreases as the reaction proceeds (fewer possible microstates), and the sign of the entropy change is negative.
Part E

• 1 point is earned for the correct explanation.

ΔG° = ΔH° − TΔS° As the temperature increases |TΔS°| will at some point exceed |∆H°|. Because both ΔH° and ΔS° are
negative, the sign of ΔG° will then change from negative to positive.

• 1 point is earned for explaining increased yield at low temperatures.

Low temperatures: The reaction is exothermic. By Le Chatelier’s principle, decreasing the temperature drives the reaction
to the right to produce more heat energy, and thus more ammonia is produced.

1 point is earned for explaining increased yield at high pressure.

High pressures: For this reaction, higher pressure is achieved by decreasing the volume of the container. As pressure
increases, the reaction equilibrium shifts in the direction that reduces the total number of particles (by Le Chatelier’s
principle). In this case, the product has fewer moles of particles than the reactants; thus product would be favored. Higher
pressure therefore results in an increase in the amount of ammonia.

0 1 2 3

The student response earns three of the following points:

• 1 point is earned for the correct explanation.

ΔG° = ΔH° − TΔS° As the temperature increases |TΔS°| will at some point exceed |∆H°|. Because both ΔH° and ΔS° are
negative, the sign of ΔG° will then change from negative to positive.

• 1 point is earned for explaining increased yield at low temperatures.

Low temperatures: The reaction is exothermic. By Le Chatelier’s principle, decreasing the temperature drives the reaction
to the right to produce more heat energy, and thus more ammonia is produced.

1 point is earned for explaining increased yield at high pressure.

High pressures: For this reaction, higher pressure is achieved by decreasing the volume of the container. As pressure
increases, the reaction equilibrium shifts in the direction that reduces the total number of particles (by Le Chatelier’s
principle). In this case, the product has fewer moles of particles than the reactants; thus product would be favored. Higher
pressure therefore results in an increase in the amount of ammonia.

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Unit 7 - Released FRQ Questions

10. Use principles of thermodynamics to answer the following questions.

a. The gas N2O4 decomposes to form the gas NO2 according to the equation below.

i. Predict the sign of ΔH° for the reaction. Justify your answer.

ii. Predict the sign of ΔS° for the reaction. Justify your answer.

b. One of the diagrams below best represents the relationship between ΔG° and temperature for the reaction
given in part (a). Assume that ΔH° and ΔS° are independent of temperature.

Draw a circle around the correct graph. Explain why you chose that graph in terms of the relationship
ΔG° = ΔH° – TΔS°.

c. A reaction mixture of N2O4 and NO2 is at equilibrium. Heat is added to the mixture while the mixture is
maintained at constant pressure.

i. Explain why the concentration of N2O4 decreases.

ii. The value of Keq at 25°C is 5.0 × 10−3 . Will the value of Keq at 100°C be greater than, less
than, or equal to this value?

d. Using the value of Keq at 25°C given in part (c)(ii), predict whether the value of ΔH° is expected to be
greater than, less than, or equal to the value of TΔS°. Explain.

Part A

i. One point is earned for the correct sign and a correct explanation.

Bonds are broken when NO2 molecules form from N2O4 molecules. Energy must be absorbed to break bonds, so
the reaction is endothermic and the sign of ΔH° is positive.

ii. One point is earned for the correct sign and a correct explanation.

AP Chemistry Page 35 of 37
 Scoring Guide

Unit 7 - Released FRQ Questions

There are two gaseous product molecules for each gaseous reactant molecule, so the product has more entropy
than the reactant. The entropy increases as the reaction proceeds, so the sign of ΔS° is positive.

0 1 2

Student earns 2/2 points

1. One point is earned for the correct sign and a correct explanation.

Bonds are broken when NO2 molecules form from N2O4 molecules. Energy must be absorbed to break bonds, so
the reaction is endothermic and the sign of ΔH° is positive.

2. One point is earned for the correct sign and a correct explanation.

There are two gaseous product molecules for each gaseous reactant molecule, so the product has more entropy
than the reactant. The entropy increases as the reaction proceeds, so the sign of ΔS° is positive.
Part B

One point is earned for the correct graph selection.

One point is earned for the explanation.

The leftmost graph should be circled.

ΔS° is positive, so as T increases, TΔS° becomes a larger positive number. At higher temperatures, you are
subtracting larger positive numbers from ΔH° to get ΔG°, so ΔG° decreases with increasing temperature.

0 1 2

Student earns 2/2 points

One point is earned for the correct graph selection.

One point is earned for the explanation.

The leftmost graph should be circled.

ΔS° is positive, so as T increases, TΔS° becomes a larger positive number. At higher temperatures, you are
subtracting larger positive numbers from ΔH° to get ΔG°, so ΔG° decreases with increasing temperature.
Part C

i. One point is earned for the correct explanation.

The reaction is endothermic. For endothermic reactions, increasing the temperature drives the reaction to the
right. This increases the equilibrium concentration of NO2 and decreases the equilibrium concentration of N2O4.

Page 36 of 37 AP Chemistry
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Unit 7 - Released FRQ Questions

ii. One point is earned for the correct choice. (No explanation required.)

Because the reaction is endothermic, at higher temperatures the reaction goes further to the right. This means that
the value of Keq at 100°C will be greater than the value of Keq at 25°C.

0 1 2

Student earns 2/2 points

1. One point is earned for the correct explanation.

The reaction is endothermic. For endothermic reactions, increasing the temperature drives the reaction to the
right. This increases the equilibrium concentration of NO2 and decreases the equilibrium concentration of N2O4.

2. One point is earned for the correct choice. (No explanation required.)

Because the reaction is endothermic, at higher temperatures the reaction goes further to the right. This means that
the value of Keq at 100°C will be greater than the value of Keq at 25°C.
Part D

One point is earned for the correct prediction.

One point is earned for the explanation.

Keq at 25°C is less than 1, hence ΔG° must be positive. And in order for ΔG° to be positive, ΔH° must be greater than
TΔS°.

0 1 2

Student earns 2/2 points

One point is earned for the correct prediction.

One point is earned for the explanation.

Keq at 25°C is less than 1, hence ΔG° must be positive. And in order for ΔG° to be positive, ΔH° must be greater than
TΔS°.

AP Chemistry Page 37 of 37